CN114574759A

CN114574759A - Ferritic stainless steel for fuel cell bipolar plates, method for controlling surface roughness, method for forming passive film and use

Info

Publication number: CN114574759A
Application number: CN202210155650.8A
Authority: CN
Inventors: 卢华兴; 席烨廷; 杨运民; 隗健
Original assignee: Shandong Industry Research Institute Of Advanced Materials Co ltd; Spic Hydrogen Energy Technology Development Co Ltd
Current assignee: Shandong Industry Research Institute Of Advanced Materials Co ltd; Spic Hydrogen Energy Technology Development Co Ltd
Priority date: 2022-02-21
Filing date: 2022-02-21
Publication date: 2022-06-03
Anticipated expiration: 2042-02-21
Also published as: CN114574759B; WO2023155264A1; CN115896896A

Abstract

The invention discloses ferritic stainless steel for a fuel cell bipolar plate, a surface roughness regulation and control method, a method for forming a passive film and application. The ferritic stainless steel includes C0.03 wt.% or less, N0.02 wt.% or less, Si 0.4 wt.% or less, Mn 0.5 wt.% or less, Cr 16 to 23 wt.%, Cu 0 to 2.0 wt.%, Mo 1.8 to 2.5 wt.%, Ni 0.2 to 2.0 wt.%, Ti 0.1 to 0.5 wt.%, Nb 0.005 to 0.5 wt.%, P0.02 wt.% or less, and S0.02 wt.% or less, with the balance being Fe and unavoidable other elements, and has a grain size of 4 to 9 grades. The high-strength steel has good corrosion resistance and conductivity, good elongation and deformability, and has economic and cost advantages.

Description

Ferritic stainless steel for fuel cell bipolar plates, method for controlling surface roughness, method for forming passive film and use

Technical Field

The invention relates to the technical field of stainless steel production, in particular to ferritic stainless steel for a fuel cell bipolar plate, a surface roughness regulating and controlling method, a method for forming a passive film and application.

Background

A fuel cell is a device that directly converts chemical energy possessed by a fuel into electric energy, and a Proton Exchange Membrane Fuel Cell (PEMFC) is one of the fuel cells. PEMFCs have been recently valued and rapidly developed worldwide due to their high power generation efficiency and non-pollution to the environment. The bipolar plate serves as a core component of the fuel cell, and plays important roles of supporting a membrane electrode structure in the fuel cell, separating hydrogen and oxygen, collecting electrons, conducting heat, providing hydrogen and oxygen channels, discharging water generated by reaction, providing a coolant flow channel and the like. With the improvement of the requirement on high volume power density of the fuel cell, the metal bipolar plate can be made into a thinner bipolar plate by adopting a stamping mode due to the higher strength and toughness of the material, and the application is increasingly wide.

However, the metal bipolar plate has poor corrosion resistance and high interface contact resistance in a hydrogen fuel cell environment, which is a very difficult problem, and a metal material with strong corrosion resistance, good conductivity and low cost is urgently needed in the industry to meet the large-scale requirements brought by the rapid development of the industry. Korean scholars in 2017 disclosed a stainless steel for a polymer fuel cell separator having excellent contact resistance and a method for manufacturing the same (KR: 013918/2017; CN:110199047B/2017), the stainless steel product of which has been currently used in modern fuel cell automobile production and the conductivity and corrosion resistance of which meet the standards set by the united states department of energy. The japanese scholars in 2010 disclose a stainless steel for fuel cells excellent in corrosion resistance for JFE and a method for manufacturing the same (CN: 102471916/2010; JP: 062739/2010), and the relevant materials are to be applied to fuel cell buses.

With the rapid development of the industry in recent years, the requirement on the product consistency is improved, and the main problems of the existing preparation technical scheme of the ferritic stainless steel bipolar plate are that the deformation capability is poor due to the problem of component design, the forming difficulty in the bipolar plate processing process is large, the bipolar plate deformation can also cause the problems of poor sealing performance and the like. Meanwhile, the cost is caused by more alloying elements. On the other hand, the stainless steel surface passive film is used as an important corrosion-resistant functional layer, and the problem of the preparation process of the stainless steel surface passive film causes that the formed passive film is thin and discontinuous, so that the corrosion resistance is poor, the growth and the components of the passive film are uncontrollable, and the conductivity and the corrosion resistance are unstable. In addition, the mainstream material of the metal bipolar plate at present contains titanium besides stainless steel, but the deformation capability of titanium as the bipolar plate material is relatively poor, the stamping difficulty is high, and the cost is much higher than that of stainless steel, which all affect the key problems of consistency, corrosion resistance, economy and the like of the bipolar plate, and the solution is urgently needed.

Disclosure of Invention

In view of the above problems in the prior art, an object of the present invention is to provide a ferritic stainless steel for a fuel cell bipolar plate, a method of controlling surface roughness, a method of forming a passivation film, and uses thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a ferritic stainless steel for a fuel cell bipolar plate, comprising, in 100 wt.% of the ferritic stainless steel:

the balance being Fe and other elements inevitably contained, preferably 0.02 wt.% or less of O and 0.1% or less of Sn, among inevitable impurities;

the grain size of the ferritic stainless steel is 4-9 grades, such as 4 grades, 5 grades, 6 grades, 7 grades or 8 grades, and preferably 6-8 grades. Therefore, the stainless steel material can be ensured to have proper manufacturability (beneficial to processes such as rolling, heat treatment and the like), and is beneficial to processing and forming the bipolar plate material and has certain economical efficiency.

C has the effect of solid solution strengthening, has low solubility in ferrite, excessive carbon is precipitated in the form of carbide, and C and Cr form carbonitride of Cr, so that intergranular corrosion and grain boundary chromium depletion of the ferritic stainless steel are caused, and the mechanical property, welding property and the like of the material are influenced. In the ferritic stainless steel of the present invention, the content of C is 0.03 wt.% or less, for example, 0.03 wt.%, 0.02 wt.%, or 0.01 wt.%, and preferably 0.02 wt.% or less.

N forms carbonitride of Cr with Cr, producing Cr-lean regions and reducing the corrosion resistance of the stainless steel. In the ferritic stainless steel of the present invention, the content of N is 0.02 wt.% or less, for example, 0.02 wt.% or 0.01 wt.%.

Si is an element useful for deoxidation. However, as the content increases, the material processability decreases. In the ferritic stainless steel of the present invention, the content of Si is 0.4 wt.% or less, for example, 0.4 wt.%, 0.35 wt.%, 0.3 wt.%, 0.25 wt.%, 0.2 wt.%, 0.15 wt.%, 0.1 wt.%, 0.08 wt.%, 0.05 wt.%, or 0.03 wt.%.

Mn is an element which is inevitably mixed in the steel, and can improve the strength of the steel in addition to a certain deoxidation effect. However, MnS as an impurity acts as a starting point of corrosion, and the corrosion resistance is lowered. In the ferritic stainless steel of the present invention, the content of Mn is 0.5 wt.% or less, for example, 0.5 wt.%, 0.47 wt.%, 0.45 wt.%, 0.4 wt.%, 0.35 wt.%, 0.3 wt.%, 0.25 wt.%, 0.2 wt.%, 0.15 wt.%, 0.1 wt.%, 0.08 wt.%, 0.05 wt.%, or 0.03 wt.%, and the like.

Cr is an essential element determining the corrosion resistance of the ferritic stainless steel, and the action of chromium and oxygen in a corrosion medium forms a thin oxide film on the surface of the steel, so that the further corrosion of a steel matrix can be prevented. However, an increase in the chromium content accelerates the formation and precipitation of the alpha and sigma phases, which causes a decrease in toughness and a significant increase in brittle transition temperature, and is disadvantageous for processing in the process of manufacturing stainless steel. In the ferritic stainless steel of the invention, the content of Cr is 16 to 23 wt.%, for example 16 wt.%, 16.5 wt.%, 16.8 wt.%, 17 wt.%, 17.5 wt.%, 18 wt.%, 18.5 wt.%, 19 wt.%, 19.5 wt.%, 20 wt.%, 20.5 wt.%, 21 wt.%, 21.5 wt.%, 22 wt.%, 22.5 wt.%, or 23 wt.%.

Cu is an element that improves the corrosion resistance of stainless steel, and can improve the cold workability of the material. In the ferritic stainless steel of the present invention, the content of Cu is 0 to 2.0 wt.%, for example, 0 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.25 wt.%, 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.5 wt.%, 0.55 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, or 2 wt.%.

Mo is another main element that improves the corrosion resistance of stainless steel. Promote the passivation of Fe-Cr alloy, and improve the corrosion resistance of steel in reducing medium, especially the local corrosion resistance of steel in chloride solution, such as pitting corrosion resistance, crevice corrosion resistance, etc. However, when the Mo content is high, a ferrite sigma phase and other brittle phases are likely to appear, which causes the toughness of the steel to be reduced and the strength to be increased, and is not favorable for processing materials. In the ferritic stainless steel of the present invention, the content of Mo is 1.8 to 2.5 wt.%, for example 1.8 wt.%, 1.85 wt.%, 1.9 wt.%, 2.0 wt.%, 2.1 wt.%, 2.2 wt.%, 2.3 wt.%, 2.4 wt.%, or 2.5 wt.%.

Ni is an element that improves the corrosion resistance of stainless steel and also acts to reduce contact resistance. In the ferritic stainless steel of the present invention, the content of Ni is 0.2 to 2.0 wt.%, for example, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.8 wt.%, 1.0 wt.%, 1.1 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.7 wt.%, 1.8 wt.%, or 2.0 wt.%.

Both Ti and Nb preferentially combine with C, N to form carbonitride, thereby suppressing the decrease in corrosion resistance due to precipitation of Cr carbonitride. However, if the content is too high, the workability is deteriorated. In the ferritic stainless steel of the present invention, the content of Ti is 0.1 to 0.5 wt.%, for example, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, or 0.5 wt.%. In the ferritic stainless steel of the present invention, the content of Nb is 0.005 to 0.5 wt.%, for example 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, or 0.5 wt.%, and the like, and Nb is preferably 0.1 to 0.4 wt.%.

In the ferritic stainless steel of the present invention, the content of P is 0.02 wt.% or less, for example, 0.02 wt.% or 0.01 wt.%.

In the ferritic stainless steel of the present invention, the content of S is 0.02 wt.% or less, for example, 0.02 wt.% or 0.01 wt.%, and preferably 0.01 wt.% or less.

In addition, in addition to the above, V may be contained in an amount of 0 to 1 wt.% and/or W may be contained in an amount of 0 to 1 wt.%, respectively, for the purpose of improving corrosion resistance. To obtain this effect, the preferred content of both elements is above 0.1 wt.%.

As a preferable technical scheme of the invention, V and W are combined with C in preference to Cr, so that the corrosion resistance of the material is improved, and the material has a synergistic effect with Nb to a certain extent; meanwhile, in order to maintain suitable material processability, the amount of Nb added is suitably reduced when V and W are added.

For the purpose of improving hot workability, 0.0002 to 1 wt.% of a rare earth metal, preferably Ce or Y, may be contained. In order to obtain this effect, it is preferable to contain 0.0005 wt.% or more.

The ferritic stainless steel has the characteristics of few alloy element types and low Cr content, and through the design of the element types and the content, the ferritic stainless steel has good corrosion resistance, conductivity and elongation and deformability, and has the advantages of economy and cost. Wherein the content of Ni is preferably 0.9-1.2 wt.%, further reducing the cost and still satisfying the above effects.

Compared with other metal material bipolar plates (such as titanium bipolar plates), the ferritic stainless steel has the advantages of low cost and better forming and processing performances.

Preferably, the surface roughness of the ferritic stainless steel is between 100nm and 700nm, the roughness is 100nm, 150nm, 170nm, 200nm, 230nm, 260nm, 300nm, 325nm, 350nm, 380nm, 400nm, 435nm, 460nm or 500nm and the like, the roughness is too small, the interface contact resistance is remarkably increased, the internal resistance of the fuel cell is increased, and the ferritic stainless steel cannot be well attached to a gas diffusion layer, so that the ferritic stainless steel is not suitable for application; the roughness is too large, the contact resistance is low, but the corrosion resistance of the material is obviously reduced, the requirement of the interior of a fuel cell and the acid environment on the bipolar plate cannot be met, the preferable range is 100-600 nm, and the further preferable range is 200-500 nm.

As a preferable technical scheme of the ferritic stainless steel, the surface of the ferritic stainless steel is provided with a passive film, and the passive film comprises a p-type passive film and an n-type passive film. The passive film has advantages in performance as an important corrosion-resistant and conductive functional layer, and the technical principle is as follows: the p-type passive film can effectively prevent the solution from contacting with the matrix to corrode, and the n-type passive film can effectively prevent the metal ions from dissolving out, so that the adverse effect of the metal ions on other core components (such as proton exchange membranes, catalysts and the like) of the fuel cell is effectively reduced, the performance of the fuel cell stack is improved, and the service life of the fuel cell stack is prolonged.

In the present invention, the p-type passivation film corresponds to the p-type semiconductor region, and the n-type passivation film corresponds to the n-type semiconductor region.

In the present invention, the p-type passivation film refers to a p-type semiconductor-type passivation film, and the n-type passivation film refers to an n-type semiconductor-type passivation film.

In the present invention, the positional relationship between the p-type passivation film and the n-type passivation film is not particularly limited, and for example, a passivation film having an inner layer of n-type and an outer layer of p-type may be used. The inner layer refers to the side of the passive film close to the stainless steel master material, and the outer layer refers to the side close to the solution.

Preferably, the molar ratio of the chromium hydroxide to the chromium oxide in the p-type passivation film is I_p[Cr(OH)₃/Cr₂O₃]，I_p[Cr(OH)₃/Cr₂O₃]Not less than 10, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 23, or 25, etc., preferably not less than 15. Excellent corrosion resistance can be obtained by optimizing the molar ratio of chromium hydroxide and chromium oxide in the p-type passivation film, the higher the ratio, the higher the hydroxide ratio, and the better the corrosion resistance.

Preferably, the molar ratio of the chromium hydroxide to the chromium oxide in the n-type passivation film is I_n[Cr(OH)₃/Cr₂O₃]，I_n[Cr(OH)₃/Cr₂O₃]Not more than 10, such as 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.5, etc., preferably less than 5. Excellent conductivity can be obtained by optimizing the molar ratio of chromium hydroxide and chromium oxide in the n-type passivation film, the lower the ratio, the higher the oxide ratio, and the better the conductivity.

Preferably, I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]>3, preferably I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]Not less than 4. Such as 3.5, 4, 5, 6, 7, 8, 9, or 10, etc. If I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]Less than or equal to 3, the comprehensive performance of the passive film can not be ensured.

In the present invention, I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]Is abbreviated as I_p/I_n。

Preferably, the thickness of the passivation film is 5 to 20nm, such as 5nm, 6nm, 8nm, 10nm, 12nm, 13nm, 15nm, 16nm, 18nm, 19nm or 20nm, and preferably 10 to 15 nm. If the passivation film is too thin (less than 5nm), the corrosion resistance is poor, and if the passivation film is too thick (more than 20nm), the conductivity is poor, and within the preferable thickness range of 10-15nm, the good corrosion resistance and the good conductivity can be better considered.

Preferably, the p-type passivation film has a thickness t_pThe thickness of the n-type passivation film is t_n，0.2<t_p/t_n<0.6，t_p/t_nSuch as 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or 0.55, etc. Under the condition, excellent interface contact resistance can be better ensured.

Preferably, in the passivation film, the inner layer is an n-type passivation film, and the outer layer is a p-type passivation film, and the following conditions are satisfied: 0.2<t_p/t_n<0.6。

In the preferred technical scheme, the passivation film structure is an inner n-type (good conductivity) and outer p-type (good corrosion resistance), the p-type passivation film is thin, and the n-type passivation film is thick, so that the structure determines that the passivation film structure has good corrosion resistance and conductivity.

In a second aspect, the present invention provides a method for controlling the surface roughness of stainless steel, the method comprising:

providing a stainless steel main material, and electrolyzing the stainless steel main material in an acid solution, wherein the polarization voltage satisfies the following formula (I) in the electrolysis process:

E≥lg D+12+pH (Ⅰ)

wherein E is polarization voltage, the unit of the polarization voltage is V, D is the grain size of the stainless steel main material, the unit of the grain size is micrometer, and the pH value is the pH value of the initial acid liquid.

The regulating method utilizes an electrolysis method to regulate the surface roughness of the stainless steel main material, has the advantage of controllable surface roughness, can pertinently regulate the surface roughness of the stainless steel according to the characteristics of a membrane electrode and gas diffusion in the proton exchange membrane fuel cell, and ensures that the bipolar plate and related components are well jointed, thereby reducing the contact resistance of a cell system, and being more suitable for the industrial application characteristics.

In the method of the present invention, if E does not satisfy formula (i), there may be no significant change in roughness, and optimal roughness cannot be achieved to match the gas diffusion layer, thereby adversely affecting the performance of the fuel cell stack.

The conditioning method may be based on the ferritic stainless steel of the first aspect. The regulation method can also be based on other stainless steel materials in the field.

Wherein "based on the ferritic stainless steel of the first aspect" means: the stainless steel main material (e.g., stainless steel sheet) is made of the ferritic stainless steel described in the first aspect, for example, by smelting, hot rolling, and cold rolling.

Preferably, the polarization voltage is 5-15V, such as 5V, 6V, 8V, 9V, 10V, 12V, 13V or 15V, etc.

Preferably, the time of the electrolysis is 10 to 300s, for example, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 100s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 200s, 220s, 230s, 240s, 260s, 280s, 300s, etc., preferably 20 to 120 s.

Preferably, the temperature of the electrolysis is 25 to 70 ℃, such as 25 ℃, 27 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, preferably 25 to 40 ℃.

Preferably, the acid solution used in the electrolysis process is sulfuric acid or a mixed acid solution of sulfuric acid and halogen acid. The preparation time of the roughness can be shortened and the roughness can be properly increased by matching the sulfuric acid with the halogen acid.

In the present invention, hydrohalic acid is abbreviated as HX acid, wherein X is halogen and X can be F, Cl, Br or I, for example.

Preferably, the hydrohalic acid is at least one of hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and is preferably hydrochloric acid and/or hydrofluoric acid.

Preferably, the concentration of the sulfuric acid is 0.1 to 14mol/L, such as 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.5mol/L, 1.7mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.5mol/L, 3.8mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, and the like, preferably 0.1 to 7 mol/L.

Preferably, the concentration of the hydrohalic acid in the mixed acid solution of sulfuric acid and hydrohalic acid is 0-3mol/L and does not contain 0, such as 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L, 1mol/L, 1.5mol/L, 1.7mol/L, 1.9mol/L, 2mol/L, 2.2mol/L, 2.4mol/L, 2.5mol/L, 2.8mol/L or 3mol/L, and the like, and preferably is not more than 0.5 mol/L.

In a third aspect, the present invention provides a method for forming a passivation film on a stainless steel surface, wherein the passivation film is prepared by an electrochemical passivation method, and the method comprises the following steps:

providing a stainless steel main material, adopting a three-electrode system, placing the stainless steel main material, a counter electrode and a reference electrode in an electrochemical passivation solution, carrying out constant potential polarization, and forming a passivation film on the surface of the stainless steel main material.

In the three-electrode system, a stainless steel main material is a sample to be processed, and the other two electrodes are respectively a counter electrode and a reference electrode. Typically, the reference electrode is between the sample to be treated and the counter electrode.

The invention forms the passive film on the surface of the stainless steel by an electrochemical passivation method, the obtained passive film has excellent performance, is compact and has good continuity, and the aims of enhancing the corrosion resistance and reducing the contact resistance can be achieved. Moreover, the passivation solution selection and method are environmentally friendly, and can ensure excellent contact resistance (meeting the U.S. DOE standard) under the condition of ultralow concentration or no hydrofluoric acid.

The electrochemical passivation method can realize the control of the components, the structure and the thickness of the passivation film, and the control of the passivation film can be realized through the electrochemical passivation process based on the specific material component design.

In the method for forming a passive film on a stainless steel surface, the stainless steel base material may be based on the ferritic stainless steel according to the first aspect, may be based on the stainless steel whose roughness has been controlled according to the second aspect, or may be based on another stainless steel material in the art.

In the present invention, the preparation method of the stainless steel main material is the prior art, and the preparation method can be performed by referring to the prior art by those skilled in the art, and by way of example and not limitation, the preparation method can be performed as follows:

preparing an ingot according to the composition of the ferritic stainless steel of the first aspect, cogging the ingot to a certain thickness (for example, 80-120 mm) to obtain a stainless steel plate, then hot rolling, heating and keeping the temperature at 1150-1200 ℃, keeping the temperature for 1.5-2.0 h, controlling the initial rolling temperature at 1100-1150 ℃, rolling the ingot to a certain thickness (for example, 2-3 mm) by 8-10 times, and controlling the final rolling temperature to be above 800 ℃.

Annealing treatment is carried out after hot rolling, the annealing temperature is 950-1050 ℃, the heat preservation time is determined according to the size of a hot rolled plate coil, and pickling treatment is carried out after hot rolling. And (4) carrying out cold rolling for 8-10 times to obtain the required thickness, and then carrying out continuous annealing for 1-3 min.

The method can ensure excellent corrosion resistance and conductivity by preparing controllable roughness on the surface of the stainless steel and then forming the passive film.

Preferably, the electrochemical passivation solution is a nitric acid solution with a concentration of 0.05-10 mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L or 10mol/L, and the concentration of the nitric acid solution is preferably 1.5-5 mol/L.

Preferably, the temperature of the electrochemical passivation is 20-85 ℃, such as 20 ℃, 25 ℃, 30 ℃, 33 ℃, 35 ℃, 38 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃, preferably 35-65 ℃.

Preferably, the anode voltage of the electrochemical passivation is not lower than 0.45V, such as 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V or 1.4V, and the like, and preferably 0.8-1.2V.

Preferably, the time of the electrochemical passivation is 5-120 min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 80min, 90min, 100min, 110min or 120min, and preferably 50-90 min.

In a fourth aspect, the present invention provides a use of the ferritic stainless steel according to the first aspect for fuel cell bipolar plates.

Compared with the prior art, the invention has the following beneficial effects:

(1) the ferritic stainless steel has the characteristics of few alloy element types and low Cr content, and through the design of the element types and the content, the ferritic stainless steel has good corrosion resistance, conductivity and elongation and deformability, and has the advantages of economy and cost. Wherein, the content of Ni can be as low as 0.2-0.5, further reducing the cost and still meeting the effects.

(2) The regulating method utilizes an electrolysis method to regulate the surface roughness of the stainless steel main material, has the advantage of controllable surface roughness, can pertinently regulate the surface roughness of the stainless steel according to the characteristics of a membrane electrode and gas diffusion in the proton exchange membrane fuel cell, and ensures that the bipolar plate and related components are well jointed, thereby reducing the contact resistance of a cell system, and being more suitable for the industrial application characteristics.

(3) The invention forms the passive film on the surface of the stainless steel by an electrochemical passivation method, the obtained passive film has excellent performance, is compact and has good continuity, and the aims of enhancing the corrosion resistance and reducing the contact resistance can be achieved. Moreover, the passivation solution selection and method are environmentally friendly, and can ensure excellent contact resistance (meeting the U.S. DOE standard) under the condition of ultralow concentration or no hydrofluoric acid.

Drawings

FIG. 1 is a graph of roughness versus interfacial contact resistance for stainless steel in accordance with one embodiment of the present invention, wherein samples 1-6 correspond, in sequence, to examples 16-21, respectively.

Fig. 2 and 3 are XPS diagrams of passivation films of stainless steel in one embodiment of the invention.

FIG. 4 is an M-S plot of a passivation film of stainless steel in one embodiment of the invention.

FIG. 5 is a plot of the carrier concentration of p-type and n-type passivation films of stainless steel in one embodiment of the invention.

FIG. 6 is a cross-sectional profile of a passivation film of stainless steel in one embodiment of the invention.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

The chemical composition (mass percent, wt.%) of the materials used for making steel are shown in table 1.

TABLE 1

The elements in the ferritic stainless steel have the following functions:

cr is an essential element determining the corrosion resistance of the ferritic stainless steel, and the action of chromium and oxygen in a corrosion medium forms a thin oxide film on the surface of the steel, so that the further corrosion of a steel matrix can be prevented. However, an increase in the chromium content accelerates the formation and precipitation of the alpha and sigma phases, which causes a decrease in toughness and a significant increase in brittle transition temperature, and is disadvantageous for processing in the process of manufacturing stainless steel.

Mo is another major element that improves the corrosion resistance of stainless steel. Promote the passivation of Fe-Cr alloy, and improve the corrosion resistance of steel in reducing medium, especially the local corrosion resistance of steel in chloride solution, such as pitting corrosion resistance, crevice corrosion resistance, etc. However, when the Mo content is high, a ferrite sigma phase and other brittle phases are likely to occur, which causes the toughness of the steel to be lowered and the strength to be increased, and is not favorable for processing the material.

C has a solid solution strengthening effect. The solubility of the chromium-free ferrite is low in ferrite, excessive carbon is precipitated in the form of carbide, intergranular corrosion and chromium depletion of grain boundaries of the ferrite stainless steel can be caused, and the mechanical property, welding property and other properties of the material are affected.

Si is an element useful for deoxidation. However, as the content increases, the material processability decreases.

Mn is an element which is inevitably mixed in the steel, and can improve the strength of the steel in addition to a certain deoxidation effect. However, MnS as an impurity becomes a starting point of corrosion, and corrosion resistance is lowered.

N and C may form carbonitride of Cr with Cr, creating Cr-lean regions that reduce the corrosion resistance of the stainless steel.

Both Ti and Nb preferentially combine with C, N to form carbonitride, thereby suppressing the decrease in corrosion resistance due to the precipitation of Cr carbonitride. However, if the content is too high, the workability is deteriorated.

Cu is an element that improves the corrosion resistance of stainless steel, and can improve the cold workability of the material.

Ni is an element that improves the corrosion resistance of stainless steel and also acts to reduce contact resistance.

The balance being Fe and unavoidable impurities.

Examples 1 to 21

And (3) preparing ingots according to the ferritic stainless steels with different steel numbers shown in the table 1, wherein the correspondence between the ingots of the various examples and the ferritic stainless steels with different steel numbers is shown in the table 2, the ingots are cogging to 100mm to obtain stainless steel plates, then hot rolling is carried out, the heating and heat preservation temperature is 1200 ℃, the heat preservation time is 2 hours, the initial rolling temperature is controlled to be 1100 ℃, the ingots are rolled to 3mm through 8 times, and the final rolling temperature is controlled to be 800 ℃. Annealing treatment is carried out after hot rolling, the annealing temperature is 1050 ℃, the heat preservation time is determined according to the size of a hot rolled plate coil, and pickling treatment is carried out after hot rolling. And then taking out the foil for air cooling, performing cold rolling again to prepare the foil with the required thickness, and performing annealing treatment of keeping the temperature at 950 ℃ for 2min to obtain a final foil sample, namely the stainless steel material.

For the stainless steel material of example 1, elongation after fracture at room temperature was measured according to the requirements of GB/T228.1-2010, and the sheet tensile standard was prepared and tested according to the standard to obtain 33.5% elongation after fracture.

The surface roughness treatment is sequentially carried out on the stainless steel material, and the material is prepared into different surface roughnesses, and the specific treatment method comprises the following steps: concentrated sulfuric acid and deionized water are adopted to prepare a sulfuric acid solution, the finally processed stainless steel material with the length and the width of 20mm is put into the sulfuric acid solution to be subjected to surface roughness treatment under different parameters, and the roughness preparation conditions are shown in table 2.

TABLE 2

After the stainless steel materials of examples 16 to 21 were subjected to roughness treatment, sampling was conducted, the surfaces of the materials were cleaned with acetone and blown dry with nitrogen, and then the surface roughness of the stainless steel was measured and recorded by a surface profiler, and the surface roughness of the material was measured and recorded at 150N/cm by an interfacial contact resistance measuring instrument²The results of the interfacial contact resistance values below are shown in table 3 and fig. 1.

TABLE 3

As can be seen from Table 3 and FIG. 1, the stainless steel material has a low interfacial contact resistance within a certain surface roughness range, and can be applied to fuel cells by properly optimizing the material, wherein the roughness is preferably between 100nm and 700nm, and more preferably between 200nm and 500 nm. Materials outside the preferred range have high interfacial contact resistance (examples 19, 20, 21) and are difficult to use in fuel cells. The roughness is too small, the interface contact resistance is obviously increased, the internal resistance of the fuel cell is increased, and the fuel cell cannot be well attached to a gas diffusion layer, so that the fuel cell is not suitable for application; the roughness is too large, the contact resistance is low, but the corrosion resistance of the material is obviously reduced, and the requirements of the interior of a fuel cell and an acid environment on the bipolar plate cannot be met.

After the above roughness treatment (in which examples 16 to 21 were subjected to surface roughness and interfacial contact resistance tests), the steel sheets of examples 1 to 21 were continuously subjected to electrochemical passivation treatment, specifically by the following treatment method:

1.6mol/L HNO at 40 ℃ for the obtained steel sheet₃In the solution, electrochemical passivation was carried out for 1h at an anodic voltage of 1.1V.

After the electrochemical passivation treatment, the sample is washed by deionized water and dried by nitrogen cold air, and is placed in a room-temperature dry environment (air) for 24 hours. The samples were then subjected to tests, specifically:

(one) determining t according to the following method_p/t_nAnd I_p/I_nThe results are shown in table 4:

the method comprises the following steps of (I) carrying out depth analysis and narrow spectrum scanning on a passivation film by using X-ray photoelectron spectroscopy (XPS), wherein an X-ray source is an Al K alpha micro-focusing monochromatic source, and scanning is carried out by adopting a CAE scanning mode, the narrow spectrum scanning energy is 30-50 eV, and the step length is 0.05-0.1 eV; and carrying out depth analysis by adopting argon ion etching, wherein the etching depth of each time is 1nm, 2nm, 5nm and 5nm respectively.

(II) the measured results were processed by software, and the content was expressed by the peak area corresponding to each phase. Since the stainless steel passivation film mainly consists of hydroxides and oxides of Fe and Cr, the XPS test mainly analyzes the phases of Fe and Cr and the contents of hydroxides and oxides thereof in the passivation film. And judging the passivation film to be a p-type semiconductor passivation film when the content of the hydroxides of Fe and Cr in the passivation film is higher than that of the oxides of Fe and Cr in the passivation film, and judging the passivation film to be an n-type semiconductor passivation film when the content of the hydroxides of Fe and Cr in the passivation film is lower than that of the oxides of Fe and Cr in the passivation film. Based on this, the amount of the passivation film can be determinedThickness t of p-type semiconductor_pAnd thickness t of n-type semiconductor_nAnd the ratio of chromium hydroxide to chromium oxide in the p-type passivation film and the n-type passivation film, thereby obtaining t_p/t_nAnd I_p/I_n。

Fig. 2 and 3 are XPS diagrams of the passivation film of the stainless steel of example 1, and fig. 2 shows the contents of hydroxides and oxides of Fe and Cr in the passivation film. As can be seen, the p-type semiconductor passivation film is about 5nm thick, while the n-type semiconductor passivation film is between 10-15nm thick. The thickness ratio t of the two passivation films_p/t_nAt 0.33-0.56, corrected t_p/t_nIs 0.55. In fig. 3, the histogram shows the contents of the hydroxide of Cr and the oxide of Cr in different thickness regions in the passivation film, respectively, and the graph shows the corresponding ratios of the hydroxide and the oxide. As can be seen from fig. 2, in the p-type passivation film, the ratio of hydroxide to oxide is 10 or more, and most is 15 or more (taking an average of 15); the ratio of the hydroxide to the oxide of Cr in the n-type passivation film is about 2 to 5, and the majority is 2 to 3 (taking an average value of 2.5). Thus, can judge I_p/I_nIs 7.

And (II) performing service performance test under the simulated fuel cell working environment: a 300h durability test was carried out at 80 ℃, pH 3 in sulphuric acid, potential 0.84V (vs. she), corrosion current density values were recorded and the material surface was measured at 150N/cm²The results of the interfacial contact resistance values are shown in Table 4.

TABLE 4

As is clear from Table 4, when the roughness treatment and the electrochemical passivation treatment were simultaneously performed, the contact resistance was 8 m.OMEGA.cm or less²The thickness ratio of p-type and n-type semiconductors is 0.2-0.6, and I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]A surface passivation film of more than 4 and a current density of less than 3 μ A ·cm^-2The interface contact resistance is less than 8m omega cm²The passivation film is demonstrated to have excellent protection and conductivity.

Meanwhile, it can be seen from table 4 that, on the basis of the unchanged electrochemical passivation treatment conditions, the surface state of the stainless steel can be changed by changing the roughness preparation conditions, and further the performance of the prepared passivation film is finally improved:

as can be seen from examples 2 to 3, in the roughness producing conditions, the concentration of the halogen acid in the range of 0 to 3mol/L is advantageous in increasing I_p/I_nLet t_p/t_nWithin a suitable range, the interface contact resistance and the corrosion current density are reduced.

As can be seen from examples 2-5, the concentration of sulfuric acid in the roughness preparation conditions is in the range of 0.1-7 mol/L, which is beneficial to increase I_p/I_nLet t_p/t_nWithin a suitable range, the interface contact resistance and the corrosion current density are reduced.

As can be seen from examples 6 to 9, the electrolysis temperature in the roughness preparation condition is in the range of 25 to 70 ℃ which is beneficial to improving I_p/I_nAnd interface contact resistance and corrosion current density are reduced.

As can be seen from the comparison between examples 10 and 11 and the comparison between examples 14 and 15, the polarization voltage in the range of 5-15V is favorable for increasing I under the roughness preparation condition_p/I_nLet t_p/t_nWithin a suitable range, the interface contact resistance and the corrosion current density are reduced.

The reason for the deterioration of the passivation film performance of example 13 in the combination of examples 10 to 13 may be that the electrolysis time is excessively long in the roughness producing condition, resulting in poor thickness ratio and composition of the p-type passivation film and the n-type passivation film.

Examples 22 to 30

The difference from example 1 is that electrochemical passivation treatment was performed with different parameters, analysis and evaluation were performed in the same manner as in example 1, and electrochemical passivation conditions and test results of example 1 and examples 22 to 30 are shown in table 5.

TABLE 5

Note: example 30 in table 5 is bare and based on example 1, no electrochemical passivation was performed.

As can be seen from table 4, the performance of the passivation film can be further improved by adjusting the parameters of the electrochemical passivation, such as nitric acid concentration, temperature, potential, and passivation time, within the specified ranges. The test results of the stainless steel sample of example 1 after being used in the fuel cell environment for a period of time show that the passivation film can reduce the contact resistance of the stainless steel interface to 8m Ω · cm²Hereinafter, the corrosion current density of the stainless steel can be maintained at a low level, exhibiting good corrosion resistance and electrical conductivity.

The Mott-Schottky (M-S) curve test was performed on example 1, example 25, example 29 and example 30 to determine the carrier concentration of the passivation film and to judge the effect of the electrochemical passivation treatment and voltage on the performance of the passivation film.

The specific M-S curve testing method comprises the following steps:

the samples were subjected to M-S curve testing in a sulfuric acid solution of pH 3 at 80 ℃ to which 0.1mol/L Na was added in order to increase the conductivity of the sulfuric acid solution₂SO₄. The M-S curve test adopts an electrochemical workstation, the test range is-1 to 1V, and the test step length is 25 mV/step. And fitting to obtain the slopes of straight line segments of the p-type passivation film and the n-type passivation film, calculating the corresponding carrier concentrations of the p-type passivation film and the n-type passivation film according to the M-S model, and determining the performance of the passivation film according to the carrier concentrations.

Fig. 4 is a graph of M-S curves of passivation films of stainless steels of example 1 (electrochemical passivation voltage 1.1V), example 25 (electrochemical passivation voltage 0.8V), example 29 (electrochemical passivation voltage 0.6V) and example 30 (no electrochemical passivation), and it can be seen from fig. 4 that p-type semiconductor regions are not evident and the passivation films mainly exhibit n-type semiconductor region characteristics in the samples without electrochemical passivation; after the polarization of the constant potential of 0.6V, the slopes of straight line segments of the p-type semiconductor region and the n-type semiconductor region are increased, but the p-type region is not obviously increased; after the constant potential polarization of 0.8V and 1.1V, the slope of the p-type semiconductor region and the n-type semiconductor region in the early stage is obviously increased. On the whole, as the constant potential polarization voltage increases, the slope of the straight line segment of the p-type semiconductor is obvious and gradually increases. The slope of the straight line segment of the n-type semiconductor region is gradually increased.

Fig. 5 is a graph showing M-S carrier concentrations of the passivation films of stainless steel of example 1 (electrochemical passivation voltage 1.1V), example 25 (electrochemical passivation voltage 0.8V), example 29 (electrochemical passivation voltage 0.6V) and example 30 (no electrochemical passivation), and it can be seen from fig. 5 that the p-type semiconductor region carrier concentration of the passivation film on the surface of the sample after electrochemical passivation gradually decreases (approximately 4 times that of the passivation film without electrochemical passivation when 1.1V is applied), and the decrease in carrier concentration indicates an increase in the denseness of the passivation film, indicating that the protective performance is improved. The carrier concentration in the n-type semiconductor region is reduced (less than 2 times at 1.1V) after electrochemical passivation, which indicates on the one hand that the protective properties of the n-type semiconductor passivation film region are increased and on the other hand that the conductivity is not significantly reduced. Therefore, the passivation film can ensure the improvement of the corrosion resistance and can not remarkably improve the contact resistance as a whole.

Meanwhile, as can be seen from the above table 4, fig. 4 and fig. 5, the composition of the passivation film can be changed by adjusting the parameters of the electrochemical passivation process, and the performance of the passivation film can be optimized. For example, the characteristics of the passivation film (see fig. 4 and 5) can be controlled by applying different voltages in the electrochemical passivation process such that the ratio t of the thicknesses of the p-type semiconductor and the n-type semiconductor in the passivation film increases with increasing potential_p/t_nGradually increasing to further improve the service performance of the stainless steel in the fuel cell stack, namely, the adjustment of the parameters can change the composition of the passive film, optimize the performance of the passive film and finally improve the adaptability of the stainless steel bipolar plate applied to the fuel cell.

The cross-sectional morphology of the passivation film of the stainless steel of example 1 was characterized by the following specific characterization method: the cross section of the sample cut by the focused ion beam is characterized by Transmission Electron Microscopy (TEM), and a passivation film cross-sectional topography (firstly, a carbon film is deposited on the outermost layer in order to protect the passivation film from being damaged in the preparation process of the focused ion beam sample) is obtained, so that as shown in fig. 6, the uppermost part is a deposited C layer, the middle part is a passivation film, and the lowermost part is a stainless steel substrate. As can be seen from the figure, the passivation film is continuous, compact and uniform in whole, has no obvious defects and has a thickness of about 12-20 nm. The outer layer of the passivation film is not flat because the passivation film at the outermost layer is subjected to dynamic growth and dissolution processes in an acid solution, and the surface of the passivation film is not flat in the acid solution.

Examples 31 to 37

The differences from example 1 are in the steel grade, whether the surface roughness treatment was performed, whether the electrochemical passivation treatment was performed, and the results are shown in table 5. Specifically, the surface roughness treatment may be directly performed after the step (1) without performing the electrochemical passivation treatment; the electrochemical passivation treatment can also be directly carried out after the step (1) without carrying out the surface roughness treatment; the surface roughness treatment and the electrochemical passivation treatment can be sequentially carried out after the step (1);

wherein, the conditions of the roughness treatment are as follows: room temperature (25 ℃), 3mol/L of H₂SO₄The sample was polarised for 50s at 10V in solution.

The conditions of the chemical passivation treatment are as follows: 1.6mol/L HNO at 40 ℃ of the steel plate obtained after the roughness treatment₃In the solution, electrochemical passivation was carried out for 1h at an anodic voltage of 1.1V.

TABLE 6

As can be seen from table 6, providing a passivation film after the roughness treatment can further enhance the protective effect, improve the conductivity, and further improve the performance.

Meanwhile, stainless steel is subjected to roughness treatment in sequence and then is provided with a passive film, the passive film on the surface of the stainless steel has good performance, the thickness ratio of the p-type semiconductor to the n-type semiconductor is 0.2-0.6, and I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]Greater than 4; and the interface contact resistance is less than 8m omega cm after the operation for a certain time²The current density is less than 3 mu A/cm²And the performance is good. In addition, no matter the passivation film is not arranged after the roughness treatment or the passivation film is directly arranged without the roughness treatment, the performance of the surface passivation film is greatly improved compared with a sample which is not subjected to the roughness treatment or the passivation film arrangement, and the subsequent long-term service test also shows that the interface contact resistance and the current density are reduced.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A ferritic stainless steel for fuel cell bipolar plates, characterized in that it comprises, in 100 wt.% of its mass:

the balance of Fe and other inevitable elements;

the grain size of the ferrite stainless steel is 4-9 grades.

2. The ferritic stainless steel for a fuel cell bipolar plate according to claim 1, characterized in that the grain size of the ferritic stainless steel is 6-8 grade;

preferably, the ferritic stainless steel further contains 0 to 1 wt.% or less of V and/or 0 to 1 wt.% of W;

preferably, the ferritic stainless steel further contains 0.0002 to 1 wt.% of rare earth metals.

3. The ferritic stainless steel for fuel cell bipolar plates according to claim 1 or 2, characterized in that the surface roughness of the ferritic stainless steel is between 100 to 700nm, preferably 100 to 600nm, and more preferably 200 to 500 nm.

4. The ferritic stainless steel for fuel cell bipolar plates according to any of claims 1-3, characterized in that the surface of the ferritic stainless steel is provided with a passive film comprising a p-type passive film and an n-type passive film;

preferably, the molar ratio of the chromium hydroxide to the chromium oxide in the p-type passivation film is I_p[Cr(OH)₃/Cr₂O₃]，I_p[Cr(OH)₃/Cr₂O₃]Not less than 10, preferably not less than 15;

preferably, the molar ratio of the chromium hydroxide to the chromium oxide in the n-type passivation film is I_n[Cr(OH)₃/Cr₂O₃]，I_n[Cr(OH)₃/Cr₂O₃]Not more than 10, preferably less than 5.

Preferably, I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]>3, preferably I_p[Cr(OH)₃/Cr₂O₃]/I_n[Cr(OH)₃/Cr₂O₃]≥4。

5. The ferritic stainless steel for fuel cell bipolar plates according to claim 4, characterized in that the thickness of the passive film is 5 to 20nm, preferably 10 to 15 nm;

preferably, the p-type passivation film has a thickness t_pThe thickness of the n-type passivation film is t_n，0.2<t_p/t_n<0.6；

6. A method for regulating and controlling the surface roughness of stainless steel is characterized by comprising the following steps:

E≥lgD+12+pH (Ⅰ)

7. The method for controlling the surface roughness of the stainless steel according to claim 6, wherein the polarization voltage is 5-15V;

preferably, the electrolysis time is 10-300 s, preferably 20-120 s;

preferably, the electrolysis temperature is 25-70 ℃, and preferably 25-40 ℃;

preferably, the acid solution used in the electrolysis process is sulfuric acid or a mixed acid solution of sulfuric acid and halogen acid;

preferably, the hydrohalic acid is at least one of hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and is preferably hydrochloric acid and/or hydrofluoric acid;

preferably, the concentration of the sulfuric acid is 0.1-14 mol/L, preferably 0.1-7 mol/L;

preferably, the concentration of the hydrohalic acid in the mixed acid solution of sulfuric acid and hydrohalic acid is 0-3mol/L and does not contain 0, and preferably is not more than 0.5 mol/L.

8. A method for forming a passive film on the surface of stainless steel is characterized in that the passive film is prepared by adopting an electrochemical passivation method, and the method comprises the following steps:

9. The method according to claim 8, characterized in that the electrochemical passivation solution is a nitric acid solution with a concentration of 0.05-10 mol/L, and the concentration of the nitric acid solution is preferably 1.5-5 mol/L;

preferably, the temperature of the electrochemical passivation is 20-85 ℃, and preferably 35-65 ℃;

preferably, the anode voltage of the electrochemical passivation is not lower than 0.45V, and preferably 0.8-1.2V;

preferably, the time of the electrochemical passivation is 5-120 min, preferably 50-90 min.

10. Use of a ferritic stainless steel according to any of the claims 1-5, characterised in that it is used for fuel cell bipolar plates.